Simultaneous determination of some trace metal impurities in high-purity sodium tungstate using coprecipitation and inductively coupled plasma atomic emission spectrometry

A method based on the combination of coprecipitation with inductively coupledplasma atomic emission spectrometry (ICP-AES) was developed for the determination of impurities inhigh-purity sodium tungstate. Six elements (Co, Cu, Fe, Mn, Ni, and Pb) were coprecipitated bylanthanum hydroxide so as to be concentrated and separated from the tungsten matrix. Effects of somefactors on the recoveries of the analytes and on the residual amount of sodium tungstate wereinvestigated, and the optimum conditions for the coprecipitation were proposed. Matrix-matchingcalibration curve method was used for the analysis. It is shown that the elements mentioned abovecan be quantitatively recovered. The detection limits for Co, Cu, Fe, Mn, Ni, and Pb are 0.07, 0.4,0.2, 0.1, 0.6, and 1.3 μg·g^(-1), respectively. The recoveries vary from 92.5% to 108%, and therelative standard deviations (RSDs) are in the range of 3.1%-5.5%.

The determination of 52 elements in marine geological samples by an inductively coupled plasma optical emission spectrometry and an inductively coupled plasma mass spectrometry with a high-pressure closed digestion method

An improved analytical method to determine the content of 52 major, minor and trace elements in marine geological samples, using a HF-HCl-HNO_3 acid system with a high-pressure closed digestion method（HPCD）, is studied by an inductively coupled plasma optical emission spectrometry（ICP-OES） and an inductively coupled plasma mass spectrometry（ICP-MS）. The operating parameters of the instruments are optimized, and the optimal analytical parameters are determined. The influences of optical spectrum and mass spectrum interferences, digestion methods and acid systems on the analytical results are investigated. The optimal spectral lines and isotopes are chosen, and internal standard element of rhodium is selected to compensate for matrix effects and analytical signals drifting. Compared with the methods of an electric heating plate digestion and a microwave digestion, a high-pressure closed digestion method is optimized with less acid, complete digestion,less damage for digestion process. The marine geological samples are dissolved completely by a HF-HCl-HNO_3 system, the relative error（RE） for the analytical results are all less than 6.0%. The method detection limits are 2–40μg/g by the ICP-OES, and 6–80 ng/g by ICP-MS. The methods are used to determine the marine sediment reference materials（GBW07309, GBW07311, GBW07313）, rock reference materials（GBW07103, GBW07104,GBW07105）, and cobalt-rich crust reference materials（GBW07337, GBW07338, GBW07339）, the obtained analytical results are in agreement with the certified values, and both of the relative standard deviation（RSD） and the relative error（RE） are less than 6.0%. The analytical method meets the requirements for determining 52 elements contents of bulk marine geological samples.

Determination of trace multi-elements in coal fly ash by inductively coupled plasma mass spectrometry

The contents of Cr, Cu, Ni, As, Cd and Pb in coal fly ash were determined by a high resolution inductively coupled plasma mass spectrometry method. The sample digestions were performed in closed microwave vessels with HNO3, HClO4 and HF. The optimum conditions for the determination were obtained. The applicability of the proposed method was validated by the analysis of coal fly ash reference material (NIST SRM 1633a). The results show that most of the spectral interferences can be avoided by measuring in the high resolution mode (maximum mass resolution R=9 000). The detection limit is from 0.05 to 0.21 μg/g, and the precision is fine with relative standard deviation less than 4.3%.

CORRECTION OF WING INTERFERENCE WITH KALMAN FILTERING IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION SPECTROMETRY

A Kalman filter was developed for correction of wing interference in ICP-AES.Modeling wing interference theoretically instead of experimentally, the filter can compensate the shift in wavelength position in scans, and therefore reduce the effect of the interference on detection limit.

A Perspective of Laser Sampling for Inductively Coupled Plasma-Atomic Emission Spectro metry for Rock and Mineral Analysis

The development of laser sampling for optical emission spectrometry is reviewed . Advantages and limitations of pulsed laser sampling are compared with those of continuous laser sampling . A novel method of laser sampling of liquid samples for inductively coupled plasma -atomic emission spectrometry has been proposed , and its analytical performance investigated.Experimental results showed that,as a method of sample introduction , laser vaporization of liquid samples enjoyed certain advantages , e.g.,much higher sensitivity, much lower detection limit and reduced sample volume , over solution nebulization . A perspective of the application of laser sampling-inductively coupled plasma - actomic emission spectrometry for rock and mineral analysis is estimated as well.

<i>In Situ</i>Analysis of Copper Alloys by Femtosecond Laser Ablation Inductively Coupled Plasma Mass Spectrometry: Constrains on Matrix Effects

Direct analysis of copper-base alloys using laser ablation techniques is an increasingly common procedure in cultural heritage studies. However, main discussions remain focused on the possibility of using non-matrix matched external reference materials. To evaluate the occurrence of matrix effects during in situ microanalysis of copper-base materials, using near infrared femtosecond laser ablation techniques (NIR fs-LA-ICP-MS), two bronzes, i.e., (Sn-Zn)-ternary and (Sn)-binary copper-matrix reference materials, as well as a reference synthetic glass (NIST-SRM-610) have been analyzed. The results have been compared to data obtained on a sulfide-matrix reference material. Similar values in relative sensitivity averages of 63Cu, 118Sn and 66Zn, as well as in 118Sn/63Cu and 66Zn/63Cu ratios were obtained, for all analyzed matrix types, i.e., copper-base-, silicate-, and sulfide-reference materials. Consequently, it is possible to determinate major and minor element concentrations in copper alloys, i.e., Cu, Sn and Zn, using silicate and sulfide reference materials as external calibrators, without any matrix effect and over a wide range of concentrations (from wt.% to ppm). Equally, Cu, Sn and Zn concentrations can be precisely determined in sulfides using homogeneous alloys (reference) materials as an external calibrator. Thus, it is possible to determine Cu, Sn and Zn in copper-base materials and their ore minerals, mostly sulfides, in a single analytical session, without requiring specific external calibrators for each matrix type. In contrast, immiscible elements in copper matrix, such as Pb and Fe show notable differences in their relative sensitivity values and ratios for different matrix-materials analyzed, implying that matrix-matched external calibrations remain to be applied for their trace quantification.

Determination of wholesome elements and heavy metals in safflower(Carthamus tinctorius L.)from Xinjiang and Henan by ICP-MS/ICP-AES

An inductively coupled plasma mass spectrometry （ICP-MS） or inductively coupled plasma atomic emission spectrometry （ICP-AES） was developed to determine 19 elements in safflower, a traditional Chinese medicinal herb from Xinjiang Autonomous Region and Henan Province of China. Totally 19 elements in safflower included heavy metals, i.e. As, Cd, Cu, Hg and Pb, and wholesome elements, i.e. Al, Ca, Co, Cr, Fe, Mg, Mn, Mo, Ni, P, Se, Sr, V and Zn. The results showed that the concentrations of heavy metals in safflower samples were both low, all of which met the national hygiene standards except for Pb in Xinjiang sample. Meanwhile, the distribution tendency of elements in the two samples was similar, which indicated that the plant might absorb given elements in a proportional way. The method can be used for the quality control of elements in safflower, and it provides a way for the determination of the contents of safflower from Xinjiang and Henan.

Elemental Content in Brown Rice by Inductively Coupled Plasma Atomic Emission Spectroscopy Reveals the Evolution of Asian Cultivated Rice

The phylogenetic relationship for classification traits and eight mineral elements in brown rice （Oryza sativa L.） from Yunnan Province in China was carried out using microwave assisted digestion followed by inductively coupled plasma atomic emission spectroscopy, and the analytical procedures were carefully controlled and validated. In general, the results show that the mean levels of K, Ca, Mg, Fe and Cu in brown rice for 789 accessions of rice landraces was distinctly lower than that of improved cultivars. They further demonstrate that Ca plays an important role in the differentiation of subspecies indica-japonica, especially to enhance adaptation of cold stress, and that five mineral elements in brown rice enhance the eurytopicity from landrace to improved cultivar. Hierarchical cluster analysis, using average linkage from SPSS software based on eight mineral elements in brown rice, showed that Yunnan rice could be grouped into rice landrace and improved cultivar, with the rice landrace being further clustered into five subgroups, and that, interestingly, purple rice does not cluster with either of the groups. Our present data confirm that indica is the closest relative of late rice and white rice, and that they constitute rice landraces together, whereas japonica is the closest relatives of non-nuda, early-mid and glutinous rice. It is further shown that japonica, non-nuda, early-mid, glutinous, white and red rice might be more primitive than indica, nuda, late, non-glutinous and purple rice, respectively.

Determination of Inorganic Elements in Paris daliensis H.Li et V.G.Souku and Paris dulongensis H.Li et S.Kuritap by ICP-OES

[Objectives] To determine 29 kinds of inorganic elements in samples of Paris daliensis H.Li et V.G.Souku and P. dulongensis H.Li et S.Kuritap produced in different regions, and to measure the content of 10 key inorganic elements: chromium(Cr), manganese(Mn), iron(Fe), copper(Cu), mercury(Hg), zinc(Zn), arsenic(As), antimony(Sr), cadmium(Cd) and lead(Pb). [Methods] The wet digestion and technique of inductively coupled plasma optical emission spectrometry(ICP-OES) were employed. [Results] Under the experimental conditions, elements were not related to each other, and many kinds of elements could be measured at the same time; toxic and heavy metals in samples of P. daliensis H.Li et V.G.Souku and P. dulongensis H.Li et S.Kuritap did not exceed the limit; Hg was not detected in all samples. [Conclusions] This method is simple, easy to operate and reproducible. It can be used for the detection of inorganic elements in P. daliensis H.Li et V.G.Souku and P. dulongensis H.Li et S.Kuritap; the heavy metals and Hg of the rhizome meet the requirements of the limit of medicinal materials.

Simultaneous determination of seven impurities in high-purity cobalt oxide by ICP-AES after matrix separation using 1-nitroso-2-naphthol as a precipitant

A method was developed for the simultaneous determination of seven trace impurities (Cd, Mn, Pb, Zn, Cu, Fe and Ni) in high purity cobalt oxide by ICP AES. The matrix effect was eliminated by preci pitation with 1 nitroso 2 naphthol. The matrix effect of cobalt on the absorptions of trace impurities, the effects of reaction time, pH value, dosage of precipitant on the formation of cobalt 1 nitroso 2 naphthol complex, the effects of hydrochloric acid on the stability of this complex and masking of elements were studied. Recoveries of the impurities in spiked sample are from 90% to 110% with a precision of 1.1% 5.0% RSD. The detection limits of the seven elements are in the range of 0.01 0.24μg/g. The method can be applied to the analysis of high purity cobalt metal, cobalt oxide and other cobalt compounds.

Study of Direct Determination of Trace Lanthanum in Biological Samples by ICP－AES Combined with Fluo

A new method for direct determination of lanthanum in solid biological materials by fluorination electrothermal vaporization ICP-AES technique with polytetrafluoroethylene(PTFE) disperser as a fluorination agent has been described. The effect of particle size on the signal intensity of La has been investigated. The vaporization behaviour of lanthanum and the main factors affecting fluorinating vaporization have been observed.Under optimum experimental conditions,the detection limit of La to this method is 2.0 ng/ml,and the RSD is 4.5%.The proposed method has been applied to determining directly trace lanthanum in solid biological standard reference materials without any chemical pretreatment,and the determined values are in good agreement with the certified ones.

Compound Ceramic Coatings Grown by Micro-plasma Oxidation on Ti-6Al-4V Alloy

Compound ceramics coatings on the Ti-6Al-4V alloy were prepared by the direct current micro-plasma oxidation （MPO） in NaAlO2 solution. The composition and morphology of the coatings were studied with the X-ray diffraction （XRD） and the scanning electron microscopy （SEM）, respectively. Inductively coupled plasma atomic emission spectrometer technique was used to analyze the solution features of Ti-6Al-4V alloy in the process of preparation. The results reveal that Al2TiO5 forms in the coatings at the initial stages of MPO reaction, and its content changes rapidly with the reaction continuing： after 20 min, the ceramics coatings are composed of α-Al2O3, 7-Al2O3 and Al2TiO5, but after 40 min, its main composition is of α-Al2O3. The content of Ti in the solution will increase when the MPO time extends, and as will Al in the anode area until, after 30 min, it reaches the maximum and keeps constant from then on. Both substrata of Ti and Al in the electrolyte join the MPO reaction at the initial stage, where the formation of Al2TiO5 happens; but as the MPO reaction prolongs, more and more Al in the electrolyte will take part in the reaction, leading to the appearance of a large amount ofAl2O3.

Determination of Palladium II in 5% Pd/BaSO₄by ICP-MS with Microwave Digestion, and UV-VIS Spectrophotometer

Determination palladiums have been reported 5% (w/w) Pd/BaSO4 known as Rosenmund Catalyst. The determination of palladium II known as Rosenmund Catalyst is always an expensive procedure usually involving procedures such as flame atomic absorption spectrophotometry, emission spectrometry, and many spectrophotometric methods. In this study, palladium II in 5% Pd/BaSO4, was synthesized and employed to develop an extractive UV-Visible Spectrophotometric, and an inductively coupled plasma mass spectrometry ICP/MS methods for the determination of palladium II. Specification for Pd is 4.85% to 5.10%;the result was 4.97% for the UV-Visible spectrophotometer and 4.90% for the ICP/MS. Both results meet the requirements.

黑果枸杞中矿物元素溶出特性研究

黑果枸杞,茄科枸杞属,富含多种矿物质元素,这对人体生长发育有重要的生物学作用。黑果枸杞作为一种药食同源的物质,为了解其营养价值、指导健康食用及进一步功能开发,有必要分析矿物质溶出特性,并进行相关性分析。黑果枸杞样品制备以硝酸和过氧化氢为消解酸,微波消解仪制备消解液,以不同温度纯水浸提制备浸泡液,试验建立了电感耦合等离子体光谱法测定消解液和浸泡液中K、Na、Ca、Mg、Zn、Fe、Mn、Cu、Li、Sr十种矿物元素含量的实验方法,并进行了矿物元素溶出特性研究及相关性分析。在优化的光谱分析条件下,十种元素线性关系好(r>0.9995)、检出限低(<0.01 mg·L^(-1))、准确度高、精密度好。加标回收率在97.2%~101.8%之间,相对标准偏差小于1.99%。实验发现,黑果枸杞中矿物元素含量丰富,含量最高的是K,其次是Na、Ca、Mg,然后是Fe、Li和Sr,含量较低的是Mn、Zn、Cu。黑果枸杞中K/Na值大于8,属于典型的高钾低钠食品。Ca、Mg、Fe、Zn、Li、Sr、Mn、Cu也是人体中多种酶、激素和维生素中不可缺少的活性因子,是一种理想的食品。黑果枸杞浸泡液中,除Li与Ca、Zn、Fe之间,Mg与Zn之间关系不明显外,其余元素间呈显著正相关或极显著正相关。表明,各矿物质元素中不存在明显的拮抗作用。矿物质元素的溶出率与浸泡时间及提取温度有关。实验采用沸水和40℃纯水浸泡黑果枸杞样品,选取浸提时间5、10和20 min三个时间点研究提取温度及时间对溶出率的影响。十种元素中K、Na、Zn溶出率最高,可能是因为三种元素多以离子形式存在,容易提取。Ca、Mg、Sr、Mn、Cu含量差异大,溶出率相近,可能是价态相近,提取效率相近。Li溶出率受提取温度影响很大,沸水浸泡溶出率是40℃温水的的1.5~2倍,Fe在微量元素中含量最高,溶出率却最低,主要是由于Fe与蛋白质结合,不易萃取。试验数据可为健康食用黑果枸杞及进一步开发利用提供理论参考。

电感耦合等离子发射光谱法与钒钼黄比色法在有效磷含量测定中的应用比较

在农业生产过程中需要对土壤中的有效磷含量以及肥料中的有效磷含量进行检测,为配方施肥提供重要依据,有效磷检测方法的准确性是评判肥料质量高低、实现配方施肥的关键。研究对电感耦合等离子发射光谱法与钒钼黄比色法这两种有效磷检测方法的灵敏度和准确度进行了比较,明确了电感耦合等离子发射光谱法在213.6 nm条件下的磷检出限为0.05 mg/L,钒钼黄比色法在400 nm检测波长的灵敏度最高,检出限为0.32 mg/L。对两种检测方法的检测准确度进行比较,结果表明电感耦合等离子发射光谱法对不同浓度的有效磷检测准确度均高于96%,其准确度受磷浓度的影响小;传统的钒钼黄比色法检测准确度受磷浓度、检测波长影响较大,对磷含量低于5 mg/L的样品检测准确度下降,且低于电感耦合等离子发射光谱法的检测准确度。研究结果认为对于未知浓度范围的样品,钒钼黄比色法在400 nm波长检测条件下的检测结果较为理想。

基于石墨消解法测定海洋沉积物中7种重金属的含量

鉴于目前常用的海洋沉积物中重金属测定的消解方法存在工作效率低、操作复杂、交叉污染、人员危险性高等问题,通过比对和参考现行规范、标准和文献资料中海洋沉积物重金属的不同消解方法,提出了全自动石墨消解海洋沉积物的方法,并以原子荧光光谱法测定汞和砷的含量,以电感耦合等离子体质谱法测定铜、铅、锌、镉、铬的含量。以6 mL盐酸、2 mL硝酸和8 mL水为消解酸,于100℃消解0.2 g样品1.5 h;消解结束后,冷却至室温,用水定容至50 mL,按照原子荧光光度计的工作条件测定汞和砷的含量。以5 mL盐酸、5mL硝酸为消解酸,先于120℃消解0.2 g样品1 h;然后加入2 mL硝酸、5 mL氢氟酸和2 mL高氯酸,于180℃继续消解4 h;消解结束后,冷却至室温,用水定容至50 mL,按照电感耦合等离子体质谱仪的工作条件测定铜、铅、锌、镉、铬的含量。结果表明:汞、砷标准曲线的线性范围分别在1.00μg·L^(-1)以内和10.0μg·L^(-1)以内,铜、铅、锌、镉、铬标准曲线的线性范围在100μg·L^(-1)以内,汞、砷、铜、铅、锌、镉、铬的检出限(3 s)为0.006~0.522 mg·kg^(-1);使用有证海洋沉积物标准物质进行验证,7种重金属测定值均在认定值的不确定度范围内,相对标准偏差(n=6)为1.4%~7.4%;对3种实际样品进行回收试验,回收率为92.5%~111%。

偏硼酸锂熔融-电感耦合等离子体发射光谱法测定铍矿石中的铍及主量元素

广泛赋存在花岗伟晶岩和热液石英脉中的铍矿石是铍最重要的矿物载体,目前铍矿石系统分析仍以传统化学法为主,影响分析效率,亟待开发一种简单高效的铍矿石中多元素分析方法。本文建立了一种基于偏硼酸锂熔融-电感耦合等离子体发射光谱(ICP-OES)测定铍矿石中铍及主量元素的定量分析方法,使用4∶1熔剂-样品比,950℃下熔融15min后,通过超声提取制备溶液。偏硼酸锂熔融法能有效地分解铍矿石中的氧化物,克服了传统酸溶或碱熔无法检测硅、钠、钾等元素的局限。本方法通过校准曲线与样品基体匹配,加入铕作内标等措施消除基体效应,实现了各元素(以氧化物计)低至0.003%~0.2%的检出限,满足铍精矿质量检测需求。对绿柱石、香花石、日光榴石样品(BeO含量范围为0.14%~13.33%)测定的相对标准偏差(RSD)小于6.83%,与混合酸酸溶分析方法的测定值相对偏差为0.06%~21.28%。通过标准物质GBW07150、GBW07151和GBW07183验证,本方法精密度和准确度均符合地质矿产实验室测试质量管理规范,适用于多种类型铍矿石样品中铍及主量元素的快速连续分析。

电感耦合等离子体发射光谱法测定土壤中有效磷的不确定度评价

为准确测定土壤中有效磷的含量,采用电感耦合等离子体光谱仪进行测定,并对测定过程中相关因素引起的不确定度进行评定。整个实验过程中不确定度来源主要包括以下5个方面:(1)样品称量时引入的不确定度u(m);(2)加入浸提液时浸提液体积V引入的不确定度u(V);(3)标准溶液配置时引入的不确定度u(C_(s));(4)标准曲线拟合引入的不确定度u(C0);(5)样品测量重复性引入的不确定度u(R)。结果表明,样品测量重复性、标准溶液配置、标准曲线拟合在整个实验中引入的不确定度影响较大。因此,在实际样品测定过程中,一定要注意对结果有影响的不确定度因素,加强质量控制,使结果准确可靠。